JPH0616754A - Resin composition, resin composition for transmission-type screen and its cured product - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a urethane (meth) acrylate, an epoxy (meth)acrylate, a specific compound, etc., giving a cured product having high refractive index and excellent mold-releasability, mold- reproducibility and memory effect and suitable for a transmission-type screen. CONSTITUTION:The composition contains (A) a urethane (meth)acrylate and/or an epoxy (meth)acrylate, (B) a compound of formula (R1 and R2 are H or CH3; X is O or S; Y1 to Y4 are H or CH3; (a) and (b) are 0-5 and average of (a+b) is 0-10), (C) a compound containing ethylenic unsaturated group other than the component B (preferably phenoxyethyl acrylate, etc.) and (D) a photopolymerization initiator. The amounts of the components A, B, C and D are preferably 20-45wt.%, 10-45wt.%, 20-50wt.% and 0.5-5wt.%, respectively. The urethane (meth)acrylate of the component A is preferably polyester urethane acrylate, etc., and the epoxy (meth)acrylate is preferably bisphenol A epoxy acrylate, etc.

Description

Detailed Description of the Invention

The present invention relates to an ultraviolet curable resin composition suitable for a transmissive screen such as a Fresnel lens and a lenticular lens used in a video projector, a projection television and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, this type of lens has been formed by a method such as a pressing method or a casting method. The former pressing method had poor productivity because it was manufactured by a cycle of heating, pressurizing and cooling. Further, the latter casting method has a problem that it takes a long time to manufacture because a monomer is poured into a mold to polymerize, and a large number of molds are required, resulting in an increase in manufacturing cost. In order to solve such a problem, various proposals have been made regarding the use of an ultraviolet curable resin composition. (For example, JP-A-61-177215, JP-A-61-248707, JP-A-61-248708, JP-A-63-163330, JP-A-63-167301,
(See JP-A-63-199302, JP-A-64-6935, etc.)

[0003]

The method for producing a transmissive screen by using these ultraviolet curable resin compositions has been successful to some extent. However, no proposal has been made to meet the demand for thinning projection televisions and the like.

[0004]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted earnest research and as a result, found a soft resin composition which cures rapidly with ultraviolet rays and has a high refractive index. The present invention has been completed. That is, the present invention relates to urethane (meth) acrylate and / or epoxy (meth)
Acrylate (A), compound (B) represented by formula (1),

[0005]

[Chemical 2]

(Wherein R ₁ and R ₂ are independently H
Or CH ₃ , X is —O— or —S—, Y _{1 to} Y ₄ are each independently H or CH ₃ , the number of a and b is 0, respectively.
The number of 5 and the average value of a + b are the numbers of 0-10. )
A resin composition containing an ethylenically unsaturated group-containing compound (C) other than the components (A) and (B) and a photopolymerization initiator (D), an ultraviolet curable resin composition for a transmissive screen, and Regarding these cured products.

In the present invention, urethane (meth) acrylate and / or epoxy (meth) acrylate (A) is used. Specific examples of urethane (meth) acrylates include polyols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, polycarbonate diol, polytetramethylene glycol, and hexamethylene diisocyanate, Organic polyisocyanates such as isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (Meth) acrylate, 2-hydroxyethyl (meth) acrylate ε-caprolactone adduct, pentaerythritol tri (meth) It may be mentioned the reaction product of a hydroxyl group-containing ethylenically unsaturated compounds such as acrylates. The production of the urethane (meth) acrylate is carried out by reacting an isocyanate group of the organic polyisocyanate, preferably 1.1 to 2.0 equivalents, at a reaction temperature of preferably 70 to 90 ° C. per 1 equivalent of the hydroxyl group of the polyol to give a urethane oligomer. It can be obtained by synthesizing and then reacting hydroxyl group-containing ethylenically unsaturated compounds, preferably 1 to 1.5 equivalents, at the reaction temperature, preferably 70 to 90 ° C., per 1 equivalent of the isocyanate group of the urethane oligomer. Preferred urethane (meth) acrylates include polyester urethane acrylate, polycaprolactone urethane acrylate, and polytetramethylene urethane acrylate.

Specific examples of the epoxy (meth) acrylate include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of bisphenol A type propylene oxide adduct, and fluorene epoxy. A reaction product of an epoxy resin such as a resin and (meth) acrylic acid can be mentioned. The reaction between the epoxy resin and the (meth) acrylic acid is carried out by (meth) acrylic acid preferably about 0.8 to 1.5 equivalents, particularly preferably about 0.9 equivalent to 1 equivalent of the epoxy group of the epoxy resin. ~ 1.
The reaction is carried out at a ratio of 1 equivalent, and as a diluent during the reaction, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, (meth) acrylic acid ester of phenylglycidyl ether, phenoxyethyl (meth) A photopolymerizable vinyl-based monomer such as acrylate, isobornyl (meth) acrylate, or dicyclopentanyl (meth) acrylate is used, and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, etc.) is used to accelerate the reaction. Benzyltriethylammonium bromide, triphenylstibine, etc.) is preferably used, and the amount of the catalyst used is preferably 0.1 to the reaction mixture.
It is 10% by weight, particularly preferably 0.3 to 5% by weight.
In order to prevent the polymerization during the reaction, it is preferable to use a polymerization inhibitor (eg, methoquinone, hydroquinone, phenothiazine, etc.). The amount used is preferably 0.01 to 1% by weight, particularly preferably 0.05 to 1% by weight, based on the reaction mixture.
It is 0.5% by weight. The reaction temperature is preferably 60-15
The temperature is 0 ° C, particularly preferably 80 to 120 ° C. Preferable examples of the epoxy (meth) acrylate include bisphenol A type epoxy acrylate and bisphenol F type epoxy acrylate.

Specific examples of the compound (B) represented by the formula (1) used in the present invention include, for example,

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

And the like.

Specific examples of the ethylenically unsaturated group-containing compound (C) other than the components (A) and (B) used in the present invention include, for example, N-vinylcaprolactam, acryloylmorpholine and 2-hydroxypropyl (meth). ) Acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylic acid ester of phenylglycidyl ether, isobornyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromobenzyl (meth) acrylate , Tribromophenyloxyethyl (meth)
Acrylate, (meth) acrylic acid ester of dipromophenyl glycidyl ether, dicyclopentanyl (meth) acrylate, polyethoxydi (meth) acrylate of tetrabromobisphenol A, bisphenol A
Polyethoxydi (meth) acrylate of bisphenol F, tetraethoxydi (meth) acrylate of bisphenol F, tricyclodecane dimethylol di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypipalinate, etc. Can be mentioned. Preferable ethylenically unsaturated group-containing compound (C) is phenoxyethyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acrylic acid ester of phenyl glycidyl ether, tribromophenyl methacrylate, tribromophenyloxyethyl acrylate, bisphenol. Examples thereof include polyethoxydiacrylate of A and the like.

The photopolymerization initiator (D) is, for example,

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

A copolymerizable photopolymerization initiator such as benzoin,
Benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, 2-methyl-1- [4-methylthio) phenyl) -2-morpholinopropan-1-one, N, N
-Dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4
-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone,
4,4'-bisdiethylaminobenzophenone, Michler's ketone and the like can be mentioned. These can be used alone or in combination of two or more. Further, together with such a photopolymerization initiator, known or commonly used photosensitizers such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine are used alone or. Can be used in combination of two or more kinds.

The proportion of each component used in the resin composition of the present invention is preferably 10 to 50% by weight of the component (A),
It is particularly preferably 20 to 45% by weight. The component (B) is preferably 5 to 50% by weight, particularly preferably 10 to 45.
% By weight. The component (C) is preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight. The component (D) is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight.

In addition to the above-mentioned components, the resin composition of the present invention also contains a release agent, an antifoaming agent, a leveling agent, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor, an antistatic agent, etc. be able to. The resin composition of the present invention can be obtained by mixing and dissolving each component. The resin composition of the present invention is particularly useful for transmission screens such as Fresnel lenses and lenticular lenses, but is also useful for various coating agents, potting agents, adhesives and the like. The cured product of the resin composition of the present invention can be obtained by irradiating the resin composition of the present invention with ultraviolet rays according to a conventional method. Specifically, the resin composition of the present invention is applied to, for example, a stamper having the shape of a Fresnel lens or a lenticular lens, a layer of the resin composition is provided, and a hard transparent substrate is bonded onto the layer. Then, in this state, ultraviolet rays are irradiated from the hard transparent substrate side by a high pressure mercury lamp or the like to cure the resin composition, and then the resin composition is peeled off. In this way the normal refractive index (23 ° C)
Of 1.55 or more, preferably 1.56 or more under a preferable condition, so that a transmission screen such as a soft Fresnel lens or a lenticular lens can be obtained.

[0026]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The evaluation in the examples was carried out by the following methods. In addition,
Parts in the synthesis examples are parts by weight. (1) Releasability: Difficulty when releasing the cured resin from the mold ○ ─── Good releasability from the mold △ ───Releasing a little difficult × ───Releasing is difficult Or, there is a lump in the mold (2) Mold reproducibility: The surface shape of the cured UV-curable resin layer and the surface shape of the mold were observed. ○ ─── Good reproducibility × ─── Poor reproducibility (3) Restorability: A nail was pressed against the surface of the cured UV-curable resin layer released from the mold to leave a mark for 30 minutes and then observed. ○ ─── No trace of nail pressing △ ─── Trace of nail pressing is slightly left × ─── Trace of nail pressing remains (4) Refractive index (23 ℃): Measurement of the refractive layer (23 ° C.) of the cured UV curable resin layer Synthesis example of urethane (meth) acrylate (A)

Synthesis Example 1 Polyester diol (polyester diol of neopentyl glycol and adipic acid, molecular weight 2000, OH
Value 56.1) 120 parts, ethylene glycol 2.48
Part, 34.8 parts of tolylene diisocyanate were charged and reacted at 80 ° C. for 10 hours after heating, then 24.4 parts of 2-hydroxyethyl acrylate and 0.1 part of methquinone were charged and reacted at 80 ° C. for 10 hours. Obtained urethane acrylate.

Synthesis Example 2 Polytetramethylene glycol (molecular weight 650, OH
Value, 172.6) 130 parts, ethylene glycol 49.
After charging 6 parts and 348 parts of tolylene diisocyanate, the temperature was raised and reacted at 80 ° C. for 10 hours, then 243.6 parts of 2-hydroxyethyl acrylate and 0.4 parts of methoquinone were charged and reacted at 80 ° C. for 10 hours to carry out urethane acrylate. Got

Examples 1 to 5 An ultraviolet-curable resin composition having a composition (numerical values indicate parts by weight) as shown in Table 1 was used in a Fresnel lens mold and a thickness of 2.5.
A Fresnel lens was obtained by injecting it between a 20 mm acrylic resin plate (provided with a primer layer) and irradiating it with ultraviolet rays to cure it.

Table 1 Actual Example 1 2 3 4 5 (A) component Urethane acrylate obtained in Synthesis Example 1 30 25 20 Urethane acrylate obtained in Synthesis Example 2 30 20 KAYARAD R-310 * 1 20 KAYARAD R-114 * 2 10 10 (B) component B-1 * 3 45 20 20 B-2 * 4 45 10 35 B-3 * 5 10 (C) component tribromophenyloxy ethyl acrylate 10 15 Phenyloxyethyl acrylate 10 10 10 10 10 Bisphenol A Poly (n = 10) ethoxydiacrylate 5 15 10 10 KAYARAD R-551 * 6 10 KAYARAD HX-220 * 7 10 10 5 (D) component Irgacure 184 * 8 3 3 3 3 3 Others LA-82 * 9 0.5 0.5 0.5 0.5 0.5 Physical properties of cured product Refractive index (25 ° C) 1.5850 1.5735 1.5780 1.5725 1.5710 Mold releasability ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restoration ○ ○ ○ ○ ○

Note * 1 KAYARAD R-31
0: Nippon Kayaku Co., Ltd., bisphenol A type poex resin (Okaka Shell Co., Ltd., Epicoat 1004) epoxy phenyl phenyl glycidyl ether acrylate 50% diluted product * 2 KAYARAD R-114: Nippon Kayaku ( Co., Ltd., epoxy acrylate of bisphenol A type epoxy resin (Yukaka Shell Co., Ltd., Epicoat 828) * 3 B-1: compound of formula (6) * 4 B-2: compound of formula (4) * 5 B-3: Compound of the above formula (3)

* 6 KAYARAD R-551:
Nippon Kayaku Co., Ltd., bisphenol A tetraethoxy diacrylate * 7 KAYARAD HX-220: Nippon Kayaku Co., Ltd., diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate * 8 Irgacure 184 : Ciba-Geigy photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone * 9 LA-82: Asahi Denka Kogyo KK, light stabilizer

As is clear from Table 1, the cured product of the resin composition of the present invention is excellent in releasability, mold reproducibility and restorability, and has a high refractive index (25 ° C.) of 1.57 or more. It was

[0034]

The cured product of the resin composition of the present invention has a high refractive index, excellent releasability, mold reproducibility and restorability, and is particularly suitable for a transmissive screen.

Claims (3)

[Claims] 1. A urethane (meth) acrylate and / or an epoxy (meth) acrylate (A), a compound (B) represented by the formula (1), and (In the formula, R ₁ and R ₂ are each independently H or CH ₃
Alternatively, X is -O- or -S-, Y _{1 to} Y ₄ are each independently H or CH ₃ , the number of a and b is 0 to 5, and the average value of a + b is 0 to 10. is there. Ethylenically unsaturated group-containing compound (C) other than the components (A) and (B)
And a resin composition containing a photopolymerization initiator (D). 2. A urethane (meth) acrylate and / or an epoxy (meth) acrylate (A) other than the compounds (B), (A) and (B) represented by the formula (1) of claim 2. A resin composition for a transmission screen, comprising an ethylenically unsaturated group-containing compound (C) and a photopolymerization initiator (D). 3. A cured product of the resin composition according to claim 1 or 2.